The present invention is directed to migration imaging members. More specifically, the present invention is directed to migration imaging members having improved optical contrast. One embodiment of the present invention is directed to a migration imaging member comprising a substrate, a first softenable layer comprising a first softenable material and a first migration marking material contained at least at or near the surface of the first softenable layer spaced from the substrate, and a second softenable layer comprising a second softenable material and a second migration marking material. Another embodiment of the present invention is directed to a migration imaging process which comprises (1) providing a migration imaging member comprising a substrate, a first softenable layer comprising a first softenable material and a first migration marking material contained at least at or near the surface of the first softenable layer spaced from the substrate, and a second softenable layer comprising a second softenable material and a second migration marking material; (2) uniformly charging the imaging member; (3) subsequent to step (2), exposing the charged imaging member to activating radiation at a wavelength to which the migration marking materials are sensitive in an imagewise pattern, thereby forming an electrostatic latent image on the imaging member; and (4) subsequent to step (3), causing the softenable materials to soften, thereby enabling the migration marking materials to migrate through the softenable materials toward the substrate in an imagewise pattern. Yet another embodiment of the present invention is directed to a process for preparing a migration imaging member which comprises (1) applying to an imaging member substrate a first softenable layer comprising a first softenable material and a first migration marking material contained at least at or near the surface of the first softenable layer spaced from the substrate, wherein additional layers are optionally situated between the substrate and the first softenable layer; (2) applying to a support a second softenable layer comprising a second softenable material and a second migration marking material, wherein additional layers are optionally situated between the support and the second softenable layer; (3) subsequent to steps (1) and (2), placing the first softenable layer in contact with the second softenable layer and causing the first softenable layer to adhere to the second softenable layer; and (4) subsequent to step (3), removing the support from the second softenable layer. Still another embodiment of the present invention is directed to a process for preparing a migration imaging member which comprises (1) applying to a first support a first softenable layer comprising a first softenable material and a first migration marking material contained at least at or near the surface of the first softenable layer spaced from the first support, wherein additional layers are optionally situated between the first support and the first softenable layer; (2) applying to a second support a second softenable layer comprising a second softenable material and a second migration marking material, wherein additional layers are optionally situated between the second support and the second softenable layer; (3) subsequent to steps (1) and (2), placing the first softenable layer in contact with the second softenable layer and causing the first softenable layer to adhere to the second softenable layer; (4) subsequent to step (3), removing the first support from the first softenable layer; (5) subsequent to step (4), placing the first softenable layer in contact with a substrate and causing the first softenable layer to adhere to the substrate, wherein additional layers are optionally situated between the substrate and the first softenable layer; and (6) subsequent to step (5), removing the second support from the second softenable layer.
Migration imaging systems capable of producing high quality images of high optical contrast density and high resolution have been developed. Such migration imaging systems are disclosed in, for example, U.S. Pat. No. 3,975,195 (Goffe), U.S. Pat. No. 3,909,262 (Goffe et al.), U.S. Pat. No. 4,536,457 (Tam), U.S. Pat. No. 4,536,458 (Ng), U.S. Pat. No. 4,013,462 (Goffe et al.), and "Migration Imaging Mechanisms, Exploitation, and Future Prospects of Unique Photographic Technologies, XDM and AMEN", P. S. Vincett, G. J. Kovacs, M. C. Tam, A. L. Pundsack, and P. H. Soden, Journal of Imaging Science 30 (4) July/August, pp. 183-191 (1986), the disclosures of each of which are totally incorporated herein by reference. Migration imaging members containing charge transport materials in the softenable layer are also known, and are disclosed, for example, in U.S. Pat. Nos. 4,536,457 (Tam) and 4,536,458 (Ng). In a typical embodiment of these migration imaging systems, a migration imaging member comprising a substrate, a layer of softenable material, and photosensitive marking material is imaged by first forming a latent image by electrically charging the member and exposing the charged member to a pattern of activating electromagnetic radiation such as light. Where the photosensitive marking material is originally in the form of a fracturable layer contiguous with the upper surface of the softenable layer, the marking particles in the exposed area of the member migrate in depth toward the substrate when the member is developed by softening the softenable layer.
The expression "softenable" as used herein is intended to mean any material which can be rendered more permeable, thereby enabling particles to migrate through its bulk. Conventionally, changing the permeability of such material or reducing its resistance to migration of migration marking material is accomplished by dissolving, swelling, melting, or softening, by techniques, for example, such as contacting with heat, vapors, partial solvents, solvent vapors, solvents, and combinations thereof, or by otherwise reducing the viscosity of the softenable material by any suitable means.
The expression "fracturable" layer or material as used herein means any layer or material which is capable of breaking up during development, thereby permitting portions of the layer to migrate toward the substrate or to be otherwise removed. The fracturable layer is preferably particulate in the various embodiments of the migration imaging members. Such fracturable layers of marking material are typically contiguous to the surface of the softenable layer spaced apart from the substrate, and such fracturable layers can be substantially or wholly embedded in the softenable layer in various embodiments of the imaging members.
The expression "contiguous" as used herein is intended to mean in actual contact, touching, also, near, though not in contact, and adjoining, and is intended to describe generically the relationship of the fracturable layer of marking material in the softenable layer with the surface of the softenable layer spaced apart from the substrate.
The expression "optically sign-retained" as used herein is intended to mean that the dark (higher optical density) and light (lower optical density) areas of the visible image formed on the migration imaging member correspond to the dark and light areas of the illuminating electromagnetic radiation pattern.
The expression "optically sign-reversed" as used herein is intended to mean that the dark areas of the image formed on the migration imaging member correspond to the light areas of the illuminating electromagnetic radiation pattern and the light areas of the image formed on the migration imaging member correspond to the dark areas of the illuminating electromagnetic radiation pattern.
The expression "optical contrast density" as used herein is intended to mean the difference between maximum optical density (D.sub.max) and minimum optical density (D.sub.min) of an image. Optical density is measured for the purpose of this invention by diffuse densitometers with a blue Wratten No. 94 filter. The expression "optical density" as used herein is intended to mean "transmission optical density" and is represented by the formula: EQU D=log.sub.10 [I.sub.o /I]
where I is the transmitted light intensity and I.sub.o is the incident light intensity. For the purpose of this invention, all values of transmission optical density given in this invention include the substrate density of about 0.2 which is the typical density of a metallized polyester substrate.
There are various other systems for forming such images, wherein non-photosensitive or inert marking materials are arranged in the aforementioned fracturable layers, or dispersed throughout the softenable layer, as described in the aforementioned patents, which also disclose a variety of methods which can be used to form latent images upon migration imaging members.
Various means for developing the latent images can be used for migration imaging systems. These development methods include solvent wash away, solvent vapor softening, heat softening, and combinations of these methods, as well as any other method which changes the resistance of the softenable material to the migration of particulate marking material through the softenable layer to allow imagewise migration of the particles in depth toward the substrate. In the solvent wash away or meniscus development method, the migration marking material in the light struck region migrates toward the substrate through the softenable layer, which is softened and dissolved, and repacks into a more or less monolayer configuration. In migration imaging films supported by transparent substrates alone, this region exhibits a maximum optical density which can be as high as the initial optical density of the unprocessed film. On the other hand, the migration marking material in the unexposed region is substantially washed away and this region exhibits a minimum optical density which is essentially the optical density of the substrate alone. Therefore, the image sense of the developed image is optically sign reversed. Various methods and materials and combinations thereof have previously been used to fix such unfixed migration images. One method is to overcoat the image with a transparent abrasion resistant polymer by solution coating techniques. In the heat or vapor softening developing modes, the migration marking material in the light struck region disperses in the depth of the softenable layer after development and this region exhibits D.sub.min which is typically in the range of 0.6 to 0.7. This relatively high D.sub.min is a direct consequence of the depthwise dispersion of the otherwise unchanged migration marking material. On the other hand, the migration marking material in the unexposed region does not migrate and substantially remains in the original configuration, i.e. a monolayer. In known migration imaging films supported by transparent substrates, this region exhibits a maximum optical density (D.sub.max) of about 1.8 to 1.9. Therefore, the image sense of the heat or vapor developed images is optically sign-retained.
Techniques have been devised to permit optically sign-reversed imaging with vapor development, but these techniques are generally complex and require critically controlled processing conditions. An example of such techniques can be found in U.S. Pat. No. 3,795,512, the disclosure of which is totally incorporated herein by reference.
For many imaging applications, it is desirable to produce negative images from a positive original or positive images from a negative original (optically sign-reversing imaging), preferably with low minimum optical density. Although the meniscus or solvent wash away development method produces optically sign-reversed images with low minimum optical density, it entails removal of materials from the migration imaging member, leaving the migration image largely or totally unprotected from abrasion. Although various methods and materials have previously been used to overcoat such unfixed migration images, the post-development overcoating step can be impractically costly and inconvenient for the end users. Additionally, disposal of the effluents washed from the migration imaging member during development can also be very costly.
The background portions of an imaged member can sometimes be transparentized by means of an agglomeration and coalescence effect. In this system, an imaging member comprising a softenable layer containing a fracturable layer of electrically photosensitive migration marking material is imaged in one process mode by electrostatically charging the member, exposing the member to an imagewise pattern of activating electromagnetic radiation, and softening the softenable layer by exposure for a few seconds to a solvent vapor thereby causing a selective migration in depth of the migration material in the softenable layer in the areas which were previously exposed to the activating radiation. The vapor developed image is then subjected to a heating step. Since the exposed particles gain a substantial net charge (typically 85 to 90 percent of the deposited surface charge) as a result of light exposure, they migrate substantially in depth in the softenable layer towards the substrate when exposed to a solvent vapor, thus causing a drastic reduction in optical density. The optical density in this region is typically in the region of 0.7 to 0.9 (including the substrate density of about 0.2) after vapor exposure, compared with an initial value of 1.8 to 1.9 (including the substrate density of about 0.2). In the unexposed region, the surface charge becomes discharged due to vapor exposure. The subsequent heating step causes the unmigrated, uncharged migration material in unexposed areas to agglomerate or flocculate, often accompanied by coalescence of the marking material particles, thereby resulting in a migration image of very low minimum optical density (in the unexposed areas) in the 0.25 to 0.35 range. Thus, the contrast density of the final image is typically in the range of 0.35 to 0.65. Alternatively, the migration image can be formed by heat followed by exposure to solvent vapors and a second heating step which also results in a migration image with very low minimum optical density. In this imaging system as well as in the previously described heat or vapor development techniques, the softenable layer remains substantially intact after development, with the image being self-fixed because the marking material particles are trapped within the softenable layer.
The word "agglomeration" as used herein is defined as the coming together and adhering of previously substantially separate particles, without the loss of identity of the particles.
The word "coalescence" as used herein is defined as the fusing together of such particles into larger units, usually accompanied by a change of shape of the coalesced particles towards a shape of lower energy, such as a sphere.
Generally, the softenable layer of migration imaging members is characterized by sensitivity to abrasion and foreign contaminants. Since a fracturable layer is located at or close to the surface of the softenable layer, abrasion can readily remove some of the fracturable layer during either manufacturing or use of the imaging member and adversely affect the final image. Foreign contamination such as finger prints can also cause defects to appear in any final image. Moreover, the softenable layer tends to cause blocking of migration imaging members when multiple members are stacked or when the migration imaging material is wound into rolls for storage or transportation. Blocking is the adhesion of adjacent objects to each other. Blocking usually results in damage to the objects when they are separated.
The sensitivity to abrasion and foreign contaminants can be reduced by forming an overcoating such as the overcoatings described in U.S. Pat. No. 3,909,262, the disclosure of which is totally incorporated herein by reference. However, because the migration imaging mechanisms for each development method are different and because they depend critically on the electrical properties of the surface of the softenable layer and on the complex interplay of the various electrical processes involving charge injection from the surface, charge transport through the softenable layer, charge capture by the photosensitive particles and charge ejection from the photosensitive particles, and the like, application of an overcoat to the softenable layer can cause changes in the delicate balance of these processes and result in degraded photographic characteristics compared with the non-overcoated migration imaging member. Notably, the photographic contrast density can degraded.
U.S. Pat. No. 4,536,458 (Ng), the disclosure of which is totally incorporated herein by reference, discloses a migration imaging member comprising a substrate and an electrically insulating softenable layer on the substrate, the softenable layer comprising migration marking material located at least at or near the surface of the softenable layer spaced from the substrate, and a charge transport molecule. The migration imaging member is electrostatically charged, exposed to activating radiation in an imagewise pattern, and developed by decreasing the resistance to migration, by exposure either to solvent vapor or heat, of marking material in depth in the softenable layer at least sufficient to allow migration of marking material whereby marking material migrates toward the substrate in image configuration. The preferred thickness of the softenable layer is about 0.7 to 2.5 microns, although thinner and thicker layers can also be utilized.
U.S. Pat. No. 4,536,457 (Tam), the disclosure of which is totally incorporated herein by reference, discloses a process in which a migration imaging member comprising a substrate and an electrically insulating softenable layer on the substrate, the softenable layer comprising migration marking material located at least at or near the surface of the softenable layer spaced from the substrate, and a charge transport molecule (e.g. the imaging member described in U.S. Pat. No. 4,536,458) is uniformly charged and exposed to activating radiation in an imagewise pattern. The resistance to migration of marking material in the softenable layer is thereafter decreased sufficiently by the application of solvent vapor to allow the light exposed particles to retain a slight net charge to prevent agglomeration and coalescence and to allow slight migration in depth of marking material towards the substrate in image configuration, and the resistance to migration of marking material in the softenable layer is further decreased sufficiently by heating to allow non-exposed marking material to agglomerate and coalesce. The preferred thickness is about 0.5 to 2.5 microns, although thinner and thicker layers can be utilized.
U.S. Pat. No. 4,970,130 (Tam et al.), the disclosure of which is totally incorporated herein by reference, discloses a xeroprinting process which comprises (1) providing a xeroprinting master comprising (a) a substrate and (b) a softenable layer comprising a softenable material, a charge transport material capable of transporting charges of one polarity and migration marking material situated contiguous to the surface of the softenable layer spaced from the substrate, wherein a portion of the migration marking material has migrated through the softenable layer toward the substrate in imagewise fashion; (2) uniformly charging the xeroprinting master to a polarity opposite to the polarity of the charges that the charge transport material in the softenable layer is capable of transporting; (3) uniformly exposing the charged master to activating radiation, thereby discharging those areas of the master wherein the migration marking material has migrated toward the substrate and forming an electrostatic latent image; (4) developing the electrostatic latent image; and (5) transferring the developed image to a receiver sheet. The process results in greatly enhanced contrast potentials or contrast voltages between the charged and uncharged areas of the master subsequent to exposure to activating radiation, and the charged master can be developed with either liquid developers or dry developers. The contrast voltage of the electrostatic latent image obtainable from this process generally initially increases with increasing flood exposure light intensity, typically reaches a plateau value of about 90 percent of the initially applied voltage even with further increase in flood exposure light intensity.
U.S. Pat. No. 5,215,838 (Tam et al.), the disclosure of which is totally incorporated herein by reference, discloses a migration imaging member comprising a substrate, an infrared or red light radiation sensitive layer comprising a pigment predominantly sensitive to infrared or red light radiation, and a softenable layer comprising a softenable material, a charge transport material, and migration marking material predominantly sensitive to radiation at a wavelength other than that to which the infrared or red light radiation sensitive pigment is sensitive contained at or near the surface of the softenable layer. When the migration imaging member is imaged and developed, it is particularly suitable for use as a xeroprinting master and can also be used for viewing or for storing data.
Migration imaging members are also suitable for other purposes, such as use as masks for exposing the photosensitive material in a printing plate for processes such as lithographic printing, and the like.
U.S. Pat. No. 5,102,756 (Vincett et al.), the disclosure of which is totally incorporated herein by reference, discloses a printing plate precursor which comprises a base layer, a layer of photohardenable material, and a layer of softenable material containing photosensitive migration marking material. Alternatively, the precursor can comprise a base layer and a layer of softenable photohardenable material containing photosensitive migration marking material. Also disclosed are processes for preparing printing plates from the disclosed precursors.
Various techniques are used to deposit the migration imaging material onto the surface of the softenable layer. One technique is described in U.S. Pat. No. 3,598,644 (Goffe et al.), and involves vacuum deposition of migration marking material onto the surface of a softenable layer by positioning a heat softened layer opposite a source of migration marking material vapors, such as selenium, which produces particles of migration marking material on the surface of the softenable layer.
Another deposition technique is described in U.S. Pat. No. 4,483,622 (Soden et al.) which teaches a multistage deposition process of evaporating selenium onto a softenable layer of a migration imaging member. This is accomplished by heating the surface of the softenable layer to soften the surface, contacting the surface at a high impingement rate in a first deposition zone with selenium vapors to form a sub-surface monolayer of spherical particles and moving the surface to a second deposition zone. At the second deposition zone the surface is contacted at a low impingement with selenium vapors which increases the size of the spherical particles and optical density while maintaining a narrow size distribution and achieving a high surface packing density.
A third deposition technique is described in co-pending U.S. Ser. No. 08/413,667, filed Mar. 30, 1995 entitled "Improved Apparatus and Process for Preparation of Migration Imaging Members". This application discloses evaporating a vacuum evaporatable material onto a substrate, there being a walled container for the vacuum evaporatable material. The walled container has a plurality of apertures in its surface, the apertures being configured so that the vacuum evaporatable material is uniformly deposited onto the substrate. A source of heat evaporates the evaporatable material from the container through the apertures onto the substrate, the surface of the container being maintained at a temperature equal to or greater than the temperature of the vacuum evaporatable material
There are various known methods for pressing two softenable layers together. U.S. Pat. No. 3,741,758 (Chrzanowski) shows a process for removing background migration material from an image member comprising a layer of softenable material and migration material in the softenable material. Once the image member is exposed, the background particles and contiguous portions are extruded and sheared by passing the image member with the softenable layer at the proper viscosity through a pressure nip where some of the softenable material is extruded in front of the nip carrying with it the unmigrated particles. A second member with a substrate and softenable layer is also extruded at the roller so that a puddle is formed across the image member which aids in the extruding process.
Yet another method for pressing two softenable layers together is disclosed in U.S. Pat. No. 3,840,397 (Amidon) which teaches a particle placing system where particulate material is placed in or on a softenable layer by pressing a donor uniformly coated with particulate matter in softenable material against a free surface of a softenable layer. The donor and free surface members are in the form of a continuous web advancing from supply rolls past a pressure roller transfer station where the donor material is pressed into contact with the free surface member. As the members continue to advance, the members are stripped apart as layers, the free surface member having picked up the particles from the donor member.
Multiple layer migration imaging systems are known as taught by U.S. Pat. No. 3,982,939 (Bean). These systems use batch coating methods to coat the various layers onto the substrate.
It is also known to laminate polymer layers with vacuum deposited metal layers in a vacuum. U.S. Pat. No. 5,260,095 (Affinito) discloses formation of polymer layers under a vacuum which improves material and surface characteristics. More specifically, this patent teaches the use of "standard" polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum. Additional layers of polymer or metal may be vacuum deposited onto the solid polymer layers in the vacuum.
While known imaging members and imaging processes are suitable for their intended purposes, a need remains for improved migration imaging members. In addition, a need remains for migration imaging members with improved optical contrast density. Further, there is a need for migration imaging members wherein the optical density of the D.sub.max areas of the imaged member is increased without a corresponding increase in the optical density of the D.sub.min areas of the imaged member. Additionally, there is a need for migration imaging members wherein the optical density of the D.sub.max areas of the imaged member with respect to ultraviolet light passing through the imaging member is increased without a corresponding increase in the optical density of the D.sub.min areas of the imaged member with respect to ultraviolet light passing through the imaging member.
There is a great need for improved processing of imaging members. In conventional film manufacturing processes, the various layers are usually applied sequentially with drying occurring between each coating step. The number of coating steps has a large impact on the manufacturing yield and consequently cost. It is also desirable to overcome the difficulties of the lamination process due to air being trapped between the two layers. The air bubbles cause defects as well as breakdown and trapping at the lamination interface. The trapped charge can sensitize the migration imaging particles when they are exposed to light which results in sporatic migration when the film is subsequently heated in the image development process.